Photographic color elements containing polymeric uv absorbers



United States Patent 3,549,374 PHOTOGRAPHIC COLOR ELEMENTS CONTAIN- IN G POLYMERIC UV ABSORBERS Hiroyuki Amano, Nobuo Tsuji, and Kazuo Shirasu, Kauagawa, Japan, assignors to Fuji Shashin Film Kaisha, Kanagawa, Japan N0 Drawing. Filed Jan. 17, 1967, Ser. No. 609,749 Int. Cl. G03c N84, N86 US. CI. 96-84 7 Claims ABSTRACT OF THE DISCLOSURE Photographic light sensitive color element containing a compound of the following group to reduce the undesired side effects of ultraviolet radiation:

wherein M represents an alkali metal; R represents an aromatic or an aliphatic bivalent residual group, such as BACKGROUND OF INVENTION The present invention relates generally to color photography and more particularly to a photographic color element capable of protecting the color image obtained by color development from the action of ultraviolet radiations.

Where a photographic image is exposed to ultraviolet rays, the image will be faded or discolored in response to the intensity and the wave length of the ultraviolet rays. Further, other materials present in a photographic element together with the materials forming the photographic image are sometimes colored by ultraviolet rays. Such action is mainly caused by the ultraviolet rays of 300-400 Nm. in wave length. In order to prevent such an action, ultraviolet absorbers are frequently incorporated in a photographic emulsion layer, an intermediate layer or a protective layer.

However, there are such drawbacks in the conventionally known ultraviolet absorbers that when they are incorporated in a photographic emulsion layer, an intermediate layer or a protective layer, almost the greater part of the ultraviolet absorbers are frequently dissolved out during photographic processing and water washing. Hence, the effect of them is weakened.

Therefore, the inventors have investigated variously to improve the above-mentioned drawback of conventional ultraviolet absorbers and as the result thereof, have found that a remarkable ultraviolet preventing effect can be obtained by incorporating in at least one of the photographic emulsion layers, intermediate layers, or protective layers of a photographic color element, a polyamide, polyurea or polyurethane each containing the recurring unit of the following structure:

where M is an alkali-l-metal, X and X are radicals providing the desired polyamide, polyurea or polyurethane, and It indicates the degree of polymerization.

The ultraviolet absorbing high-molecular materials to be used in this invention will be explained in detail.

-When a 4,4-diamino-stilbene-2,2'-disulfonate having the structural formula soar som is caused to react with diisocyanate, dicarboxylic acid or its derivative, or dichloro-carbonic acid ester, the corre-' sponding polyurea, polyamide or polyurethane having the aforementioned stilbene structure is obtained, which acid) or an aliphatic dicarboxylic acid Polyurethane $03M $03M Polyurethane wherein M represents an alkali metal; R represents an aromatic or an aliphatic bivalent residual group, such as,

Further, as the dichloro-carbonic acid ester there may be employed a dichloro carbonic acid ester of an aliphatic diol, such as,

ClCOO(CH CH O )-COCl(n=24) or a dichlorocarbonic acid ester of an aromatic diol represented by ClCOO-ArOCOCl (wherein Ar represents an aromatic residual group). For example, there may be illus trated the following compounds:

Further, the above-mentioned polyurethane having the stilbene structure which can be adopted in this invention may be prepared by the reaction of a di-isocyanate and a metal salt of 4,4'-dioxystilbene-2,2-disulfonie acid having the formula and in which R and R are hydrogen atoms or alkyl radicals containing up to 5 carbon atoms, and tCHflp, or +CH CH O+qCH CH in which p is an integer from 1 to 10 and q is an integer from 1 to 3; and n shows the polymerization degree.

These polymeric compounds may be easily prepared by conventional methods. For example, the above-mentioned polyurea type compounds may be prepared as follows: that is, sodium 4,4-diamino-stilbene-2,2'-disulfonate is dissolved in formamide, and when a dimethyl formamide solution of diisocyanate in an aquimol amount as that of the diamine is added slowly to the solution while cooling the solution with vigorous stirring, the viscosity of the solution is gradually increased (at a temperature lower than 30 C.). The product is then precipitated with a large quantity of acetone to provide light yellow-brown polyurea. The polyamide type compounds may be easily obtained by using an ordinary interfacial condensation method.

The above mentioned high molecular ultraviolet absorber of this invention may be used as follows: that is, the high molecular ultraviolet absorber is dissolved in water to provide an aqueous solution of 0.15% by weight of the material, and to the aqueous solution there is added slowly an aqueous gelatin solution. The proportion of the high molecular ultraviolet absorber is preferably 10500 g. per 1 kg. of gelatin. The thus prepared mixture of gelatin and the high molecular ultraviolet absorber is applied to a photographic element as an ultraviolet preventing layer in the form of a protective layer or an intermediate layer. Further, the high molecular ultraviolet absorber of the instant invention may be directly incorporated in a photographic silver halide emulsion layer and in this case, the above defined addition amount is also preferable.

With regard to the influence of the molecular weight of the high molecular ultraviolet absorber in this invention, a better ultraviolet preventing effect can be obtained when the intrinsic viscosity of the high molecular ultraviolet absorber of this invention in formamide at 30 C. is about ODS-2.0.

In addition, the above-mentioned photographic emulsion is the usual gelatino silver halide emulsion, but the present invention may also be effectively applied in the case where protective colloid other than gelatin is employed, such as polyvinyl alcohol and polyvinyl acetal.

Now, the following typical examples illustrate the results of fading prevention and the diffusion resistance for photographic color images obtained by using the high molecular ultraviolet absorbers of the present invention, but it should be understood that the invention shall not be limited to these examples.

EXAMPLE 1 dicarboxy-u-(4- stearoylamido-benzoyl) acetanilide. The

Compound 1 FNHCH=CHNHCONH NHCO l S O Na SOaNa HsC- S Na SOaNa Compound 41 I I /D SOBNQ- SOsNB H- and coupler was added as an alkaline aqueous solution. There- Compound 5 I I N\/N SOaNa SOaNB I OH O In compounds 1-4, n indicates the degree of polymafter, a green-sensitive silver chloro-bromide emulsion erization. containing a magenta coupler, 1-(3-sulfo-4-phenoxy- Into 100 g. of a 4% aqueous solution of each of Comphenyl)-3-sterar0yl-5-pyrazolone, and a red-sensitive pounds 14 of this invention and Compound 5 of a conr silver chloro-bromide emulsion containing a cyan couventional ultraviolet absorber there was added gradually pler, N-n-octadecyl-l-hydroxy 4 sulfo-Z-naphthamide 1 kg. of a 4% aqueous solution of gelatin and the result- Were applied to the thus formed blue-sensitive emulsion ing emulsion was applied to the surface of a film support layer in order. Then, a protective layer of 2.0 microns and dried to provide a filter layer of 2.0 microns in thickin thickness was further applied thereto. The protective ness. Regarding the prepared film having the filter layer layer was formed by applying 1 kg. of an aqueous gelacontaining each compound, the state of each compound tin solution containing 100 g. of a. 4% aqueous solution after subjecting the film to water washing (A), washing of one of the high molecular ultraviolet absorbers of this with an aqueous solution of 3% sodium carbonate (B), invention having the structure 0f Compounds 1-4 shown or complete photographic processings (C) was observed, 111 Ex mple 1. p the results of which are shown in the following table. After exposure, the thus P pared color pri P p was subjected to developing in a developer containing Reduction in transmission density (370 n.n:t.), percent N-ethyl-N-fi-hydroxyethyl p phenylene diamine, stopfixing water-washing bleach-fixing Water-washing o c C o C 3 Time ouiid 1 ouiid 2 ouiid a ourid 4 pOuI?( 1 5 hardenlng, water-washing and drying. Thereafter, thus (A) 30 mm 5 7 5 7 85 processed printing paper was exposed for 20 hours by (10:: 2hrs 7 1o 7 1o 95 means of an Xenon tester and then the reduction in color gg 2g g g g g 3% density was measured. The results are shown below.

The Xenon tester which was used in the fading experiment had a light source having a spectral distribution It will be understood from the above results that while and lntenslty very similar to those of sun light.

a low molecular conventional ultraviolet absorber having w diffusing P p Such a$,C0mP0l1I1d 5 is almost FADING PERCENTAGE or COLOR IMAGE AFTER EX- pletely dissolved olf from the gelatin layer during the POSURE T0 N N T T R F R 20 HOURS washing step and complete photographic processing steps, Addition compounds, percent the high molecular Compounds 1-4 of the present inven- Color Com- Com- Com- Comt1on are scarcely dissolved off and have good diffusion in age None poundl pou11d2 pound3 pound4 I resistance. The complete photographic processing in the Cyan 40 10 15 10 10 above experiments means the steps commonly employed Magenta 20 o 2 3 1 in color paper processing, namely, the steps of color 15 20 15 15 development, water-washing, fixing, water-washing, bleach-fixing, Water-washing, hardening, water-washing As is seen from the experimental results, the fading and drying. of the color image was prevented or reduced by using Moreover, other high molecular compounds roprethe ultraviolet absorber 0f the present invention. Further, sented by the above-mentioned structural formulas (1-4) as could be anticipated naturally, When the g m uhaving differe t hi h molecular i h h d almost lar ultraviolet absorber of this invention was incorpated th 53mg ff as th b i d compounds as in an intermediate layer between a first silver halide emulultraviolet absorbers when their intrinsic viscosity in SiOIl layer and a Second Silver halide emulsion layer, f id at 30 C was i h range f ()5.2 in an intermediate layer between a second silver halide A PLE 2 emulsion layer and a third silver halide emulsion layer, EX M instead of being incorporated in the protective layer, the To a baryta paper was applied a blue-sensitive silver fading of the color image in the layer below the interiodobromide emulsion containing a yellow coupler, 3,5- mediate layer containing the ultraviolet absorber was prevented or reduced. Moreover, when a film base was used instead of the baryta paper, almost the same results were obtained.

EXAMPLE 3 To a baryta paper were applied the blue-sensitive silver halide emulsion containing the yellow coupler as in Example 2, and the green-sensitive silver halide emulsion containing the magenta coupler as in Example 2, as bottom and middle layers respectively, and as a top layer there was applied the red-sensitive silver halide emulsion containing a cyan coupler, as in Example 2, and a high molecular ultraviolet absorber of this invention having the formula shown in Example 1 in an amount of 50 g. of 4% solution per 1 kg. of emulsion to provide a multilayered light-sensitive color element.

After exposure, the thus prepared light-sensitive element was subjected to developing, stop-fixing, water- Washing, bleach-fining, water-washing, hardening, water- Washing and drying. Thereafter, thus processed lightsensitive element was exposed for 20 hours to a xenon tester, as in Example 2, and then the reduction in color image density was measured. The results of the test are as follows:

FADING PERCENTAGE OF COLOR IMAGE AFTER EX- POSURE TO XENON TESTER FOR 20 HOURS Addition compound, percent Com- Com Coni- Com- None pound 1 pound 2 pound 3 pound 4 As is seen from the experimental results, a very large ultraviolet preventing effect was obtained by incorporating directly in a silver halide emulsion layer the high molecular ultraviolet absorber of the present invention without forming a separate ultraviolet filter layer. When a film base was used as the support instead of the baryta paper, almost the same results were obtained.

What is claimed is:

1. A color photographic paper which comprises a baryta paper bearing thereon at least one light-sensitive silver halide emulsion layer and a gelatin layer on the uppermost light-sensitive silver halide emulsion layer, said gelatin layer having incorporated therein, as an agent to reduce the undesired effects of ultraviolet radiation, a compound selected from the group consisting of compounds having the following recurring structure:

M is an alkali;

8 R is an aromatic or aliphatic bivalent radical selected from the group consisting of;

in which R and R are selected from the group consisting of hydrogen atoms, alkyl radicals containing up to 5 carbon atoms, (-CHfi in which p is an integer from 1 to 10, and

in which q is an integer from 1 to 3;

n is the polymerization degree, and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in formamide at 30 C. is from 0.05 to 2.0.

2. The color photographic paper as claimed in claim 1, wherein said compound is a polyurea containing the recurring structure:

l S 0 M SOaM wherein M is an alkali metal; R is a bivalent organic radical; and n. is the degree of polymerization.

3. The color photographic paper as claimed in claim 1 wherein said compound is a polyamide containing the recurring structure:

wherein M is an alkali metal; R is a member selected from the group consisting of aromatic and aliphatic bivalent residual groups; and n is the degree of polymerization.

4. The color photographic paper as claimed in claim 1 wherein said compound is a polyurethane containing the recurring structure:

wherein M is an alkali metal; R is a member selected from the roup consisting of aromatic and aliphatic bivalent residual groups; and n is the degree of polymerization.

5-. The color photographic paper as claimed in claim 1 wherein said compound is a polyurethane containing the recurring structure:

SOsN $03M wherein n is the polymerization degree and wherein said polymerization degree is such that the intrinsic viscosity of said polymer in forrnamide at 30 C. is from 0.05 to 2.0, and wherein from 10 to 500 g. of said compound is incorporated in said gelatin layer per 1 kg. of gelatin.

S OsNa S OaNa References Cited UNITED STATES PATENTS 3,269,840 8/1966 Pattyn et a1. 96-82 2,882,157 4/1959 Thompson et a1. 96-87 FOREIGN PATENTS 867,539 5/1961 Great Britain 96-87 RONALD H. SMITH, Primary Examiner US. Cl. X.R. 

